I

THE ENGINEERING PROPERTIES OF

ELECTROLESS NICKEL COATINGS
Electroless nickel is a term used to describe plating of a
nickel-phosphorus coating onto a suitable substrate by chemical
reduction. Unlike electroplated coatings, electroless nickel
is applied without an externally applied electric current.
Instead, the coating is deposited onto a part's surface by
reducing nickel ions to metallic nickel with sodium hypophos-
phite. This chemical process avoids many of the problems
associated with most metallic coatings and provides deposits
with many unique characteristics.
As applied, electroless nickel coatings are uniform, hard,
relatively brittle, lubrious, easily solderable and highly
corrosion resistant. They can be precipitation hardened to
very high levels through the use of low temperature treat-
ments, producing wear resistance equal to that of commercial
hard chrome coatings. This combination makes the coating
well suited for many severe applications and often allows it
to be used in place of more expensive or less readily avail-
able alloys. The engineering properties of electroless
nickel deposits, and how they relate to the use of the coat-
ing, are discussed in the following sections.
STRUCTURE
Hypophosphite reduced electroless nickel is one of the very
few metallic glasses used as an engineering material. Depend-
ing onthe formulation of the plating solution, commercial
coatings may contain 5 to 12 percent phosphorus dissolved in
nickel, and as much as 0.25 percent other elements. The struc-
ture of these coatings depends upon their composition. Coatings
containing up to 5 percent phosphorus consist of crystalline S
nickel with phosphorus in solid solution. Those with phosphorus
contents between 5 and percent, contain a mixture of a and S
phases and are partly crystalline. Coatings containing more
than percent phosphorus consist only of a phase nickel-
phosphorus and are normally amorphous to x-rays. These high
phosphorus deposits have no crystal structure or separate
phases
j
' 2 ' 3 . Electron diffraction studies of deposits
have confirmed their lack of crystal structure at magnifica-
tions up to 150,000
4

The continuity of electroless nickel coatings also depends upon
composition. Coatings containing more than 10
percent phosphorus and less than 0.05 percent of impurities are
typically continuous. A cross sectional view of one of these
is shown in Figure 1.
Steel substrate
Copperoverplate
75 llm thick
coating
phosphorus coatings, and especially those applied from
baths stabilized or brightened with heavy metals or sulfur
compounds, are often porous. These deposits consist of
columns separated by cracks and holes. The presence of such
discontinuities has a severe effect on the deposit's proper-
t:i;ces:YLespecia,lly on its ductility and corrosion resistance.
this type of deposit is shown in Figure 2
1
' 2 ' 5 ' 6 .
F'IGUREI
Cross sectional
view of a 75 llm
thick
Electroless Nickel
t.,
',,400X magnification.
',Etched in 2% nital.

sectional
viE;!w of a 25 llm
''thick electroless
nickel containing
approximately 8
percent phosphorus
and 0.15 percent
cadmium and lead.
400X magnification.
Etched in 2% nital.
FIGURE 2
, c'
---"---- ---- -- -- ---- ----
Lower phosphorus and heavy metal stabilized deposits also frequently
appear to have a laminar structure parallel to their substrate. One
of this type of coating is shown in Figure 3. These laminations
result from variations in the phosphorus content of the different
layers of the coating, which in turn are due to changes in the pH
or stabilizer content of the bath during plating. The more sophis-
ticated complexing and stabilizing systems used to apply high phos-
phorus deposits, eliminate these variations and produce the more
homogeneous structure shown in Figure 1
2
, 4 , 5 , 7 .
FIGURE 3
Cross sectional view of a laminar
15 thick electroless nickel
containing 7 to 9 percent phosphorus
and small amounts of sulfur. The
tulip shaped area is the result of
a particle of sand or blasting media
embedded in the deposit during
plating. The coating was subse-
quently lapped, which removed the
protrusion produced by the particle.
1000X magnification.
Etched in 10% oxalic acid at 6 volts.
As electroless nickel deposits are heated to temperatures abov&
220
0to
260C (420 to 500F) structural changes begin to occur ;
First, coherent and then distinct particles of nickel phosphite
(Ni
3P)
form within the alloy. Then at temperatures above 320C
(600
oF)
the deposit begins to crystallize and to lose its amor-
phous character. With continued heating the nickel phosphite
particles conglomerate and a two phase alloy forms. With coat-
ings containing more than 8 percent phosphorus a matrix of Ni3P
forms, while almost pure nickel is the predominate phase in lower
phosphorus deposits. These changes cause a rapid increase in the
hardness and wear resistance of the coating, but cause its cor-
rosion resistance and ductility to be reduced. A cross sectional
view of a fully hardened, coating is shown in Figure 4
1
, 2 , 5 ,
7,8. Heating also causes the deposit to shrink and can result in
cracking through the coating to the substrate, 9.
FIGURE 4
Cross sectional view
of a 25 thick,
coating after heat treat-
ment at 400C for 24 hours.
lOOOX magnification.
Etched in 5% Cr03 at
6 volts.
with prolonged heat treatment at high temperatures phosphorus
from the region near the interface will diffuse into the sub-
strate. This can be helpful in obtaining adhesion on passive
metals like titanium or stainless steel. On mild steel, a
nickel-iron intermetallic layer between the coating and the
substrate can be produced by 4 hour heat treatments at temp-
eratures above 650C (1200
oF).
This layer provides a very
wear resistant surface, and in some environments will increase
the corrosion resistance of the coating
2,5,7,8.
INTERNAL STRESS
The internal stress in electroless nickel coatings consists
of two components--a thermal stress due to the difference in
thermal expansion between the coating and the substrate and
a structure stress due to structural mismatch within the
deposit caused by non-homogeneity. Both are primarily a
function of the coating's composition. As illustrated by
Figure SID, on steel the stress in coatings containing more
than 10 percent phosphorus is neutral or compressive. with
lower phosphorus deposits, however, tensile stresses of 15
to 45 MPa (2 to 6 ksi) occur. The high level of stress in
these coatings promotes their cracking and
FIGURE 5
Effect of phosphorus
content on the internal
stress of electroless
nickel deposits on
steel.
15
";;;
C-
o
10
0
0
...
Vl"
5
Vl
w
Tensile
a:
0
I-
Vl
Compressive
...J
5
z
a:
w
10
I-
z
15
5 6 7 8 9 10 11 12 13
PHOSPHORUS CONTENT, PERCENT
The structural changes during heat treatment at temperatures
above 220C (420F), cause a volumetric shrinkage of up to
4 to 6 percent within electroless nickel deposits. This
increases tensile stress or reduces compressive stress in
the coatings 2,8,9.
Deposit stress is also increased by the co-deposition of
orthophosphites or contaminants, or by the ~ r s n of excess
complexing agents in the plating solution 9, 1. Even small
quantities of some metals can produce a severe increase in
stress. For instance, the addition of only 5 mg/l of bismuth
and antimony to most baths will cause the deposit stress to
increase to as much as 350 MPa (50 ksi) tensile. High l v l s ~
of interal stress also reduce the coating's ductility and
increase its porosity 2,9 .
UNIFORMITY
One especially beneficial property of electroless nickel is
its uniform coating thickness. With electroplated coatings,
thickness can vary significantly depending upon the part's
configuration and its proximity to the anodes. Not only can
these variations effect the ultimate performance of the coating,
but they can also cause additional finishing to be required
after plating.
------- _ _ ~
With electroless nickel the plating rate and coating thick-
ness are the same on any section of the part exposed to fresh
plating solution. Grooves, slots, blind holes, and even the
inside of tubing will have the same amount of coating as the
outside of a part. This is illustrated by Figure 6 which shows
the uniform thickness on the internal threads of a small spray
nozzle.
FIGURE 6
An example of the uniformity
of electroless nickel coatings.
Unlike the copper overplate,
the 25 vm thick electroless
nickel coating reproduces the
profile of the internal threads
of the part. The substrate is
leaded steel.
lOOX magnification.
Etched in 1% picral.
Because of its uniformity, often the overall finishing cost of
a part will be less with electroless nickel than with electro-
plated coatings, even though the material cost of the process
is higher. For example, the substitution of electroless nickel
for hard chromium on many of the cylinders and rolls used in
the printing and textile industries has not only reduced the
cost of plating by 40 percent, but also has allowed 55 percent
of the grinding time to be saved
1 2

--- --------------- ~ ~ ~ ~ ~
With electroless nickel, coating thickness can be controlled
to suit the application. Coatings as thin as 2 ~ ~ m (0.1 mil)
are commonly applied for electronic components, while those
as thick as 75 to 125 ~ m (3 to 5 mils) are typical for corrosive
environments. Coatings thicker than 250 ~ m (10 mils) are used
for salvage or repair of worn or mismachined parts
5.
ADHESION
The adhesion of electroless nickel coatings to most metals
is excellent. The initial replacement reaction, which
occurs with catalytic metals, together with the associated
ability of the baths to remove submicroscopic soils, allows
the deposit to establish metallic as well as mechanical
bonds with the substrate. The bond strength of
coatings to properly cleaned steel has been found to be 400
MPa (60 ksi) or morel 3. The adhesion to aluminum and alumi-
num alloys is less, but usually exceeds 300 MPa (40 ksi)2,5,7:
With non-catalytic or passive metals, such as stainless
steel, an initial replacement reaction does not occur and
adhesion is reduced. with proper pretreatment and activa-
tion, however, the bond strength of the coating normally is
at least 140 MPa (20 ksi)2,5,7. The adhesion to copper aloys
is usually between 300 and 350 MPa(40 and 50 ksi)2.
With metals such as aluminum it is common practice to bake
parts after plating for 1 to 4 hours at 130+ 200C (270
to 400F) to increase the adhesion of the coating. These
treatments relieve hydrogen from the part and the deposit and
provide a very minor amount of codiffusion between the coat-
ing and substrate. They are most useful where pretreatment
has been less than adequate and adhesion is marginal. With
properly applied coatings, baking will have only a minimal
effect upon bond strength 2,5,8
MELTING POINT
Electroless nickel is an eutectic alloy with a wide melting
range. Unlike a pure compound, it does not have a true
melting point. This is illustrated by the phase diagram for
nickel-phosphorus alloys shown in Figure 7 1 ~
Jlom-t:P
If! J(}
'0
I'
I I
11/SZ'
'0\
\

"
"
'0

:;;;-
;;;: '"
'tl
+

fl15'
'\

ffltJ'
'0
I i fill>
'\
SC/JI1;elre \
,II I


j,
\
l!1IJ' 18
/"'
"6
88tJ' I
00
110<J-"
c
:0
00
Ni .. Ni.jl'
'I
1So.
1'10.
900
800
Phase diagram for nickel-
phosphorus alloys.
FIGURE 7
S 10 1S
6"1"'-"1'
JS
The melting range for electroless nickel coatings varies
depending upon the phosphorus content of the deposit.
All electroless nickel coatings begin to melt at approxi-
mately BBOoC (1620
DP),
which is the eutectic temperature
for nickel phosphide (Ni
3P).
The temperature at which the
coating is completely liquid, however, increases with de-
creasing phosphorus content from about BBODC (1620
Dp)
at
11 percent -- the eutectic point -- to approximately 1450C
(2640
DP)
for pure nickel. Thus, the melting range becomes
wider as the phosphorus content is reduced.
Practically this means that all commercial coatings contain
large quantities of liquid material at temperatures above
BBODC (1620
DF).
For example, at 900
DC
(1650
DF)
coatings
containing 5, B and percent phosphorous are 46, 74 and
100 percent melted.
PHYSICAL PROPERTIES
The density of electroless nickel coatings is inversely
proportional to their phosphorus content. As shown in
Figure B, density varies from about B.5 gm/cm
3
for very
low phosphorus deposits, to 7.75 gm/cm
3
contain-
ing about percent phosphorus 2,7,15,16,17.
---------
_ ~ _
.0
K-
''\
.6
-,
.4
~
2
-,
.0
-:
a
~
6
,'"
7
FIGURE 8
Effect of deposit
phosphorus content
on the density of
electroless nickel.
10 12
Phosphorus content, "{,
The thermal and electrical properties of these coatings also
vary with composition. For high phosphorus coatings
electrical resistivity and thermal conductl-
vity are generally about 9 0 ~ ~ c m and 0.08 Wjcm-OK (4.6 Btuj
ft-hr-oF) respectivelylB,19. Accordingly, these coatings are
significantly less conductive than conventional conductors
such as copper.
Because of the relatively thin layers used, however, for most
applications rho r09istance of electroless nickel is not
significant. coatings are being successfully used for
such applications as exchanger tubing and electrical switches
and contacts.
Heat treatments precipitate phosphorus from the alloy and
can increase the conductivity of electroless nickel by 3 to
4 times 2,7. The formulation of the plating solution can
also affect conductivity. Tests with baths complexed with
sodium acetate and with succinic acid showed electrical
resistivities of 61 and 804 ~ ~ c m respectively2.
Phosphorus content also has a strong effect on the thermal
expansion of electroless nickel. This is shown in Figure 9,
which is based on deposit stress measurements on different
substrates 10. The coefficient of thermal expansion of
coatings is approximately equal to that of steel.
_ _ ~
FIGURE 9
11 1D
Phosphorus content, %
,
5
....

'<, 1
0
<,
.............
,
5
I-.......
~
8
r-...
,
Effect of deposit
phosphorus content on
the coefficient of thermal
expansion on electroless
nickel.
As deposited, coatings containing more than 10 percent
phosphorus are completely non-magnetic. The magnetic
susceptibility of deposits is on the order of 10-
4
mks
at ambient temperature. Lower phosphorus coatings, however,
have some magnetic susceptibility. The coercivity of 3 to
6 percent phosphorus coatings is about 20 to 80 oersteds,
while that of deposits containing 7 to 9 percent phosphorus
is typically 1 to 2 oersteds. Heat treatment at temperatures
above 260C (500F) improve the magnetic response of all
electroless nickels and can provide coercities of about 100
to 300 oersteds 20,21.
MECHANICAL PROPERTIES
The mechanical properties of electroless nickel deposits
are similar to those of other glasses. They have high
strength, limited ductility and a high modulus of elas-
ticity. The ultimate tensile strength of most coatings
exceeds 700 MPa (100 ksi). This is equal to that of many
hardened steels and allows the coating to withstand a
considerable amount of abuse without damage. The effect
of phosphorus content upon the strength and strain at
fracture of electroless nickel deposits is shown in
Figure 10
2 2

----- ---------
FIGURE 10
.024
.020
.012
.016
.008
0.028
0.032
.004
10
.......

0
0 0
0
/
0
V
V
0 0
.....
,/
0
V
0
0
,J
0
0 0 10
30
20
70
BOO
"
Effect of phosphorus
content on strength
and strain at fracture
of electroless nickel
deposits.
Phosphorus content, %
The ductility of electroless nickel coatings also varies
with composition. The ductility of coatings is
about 1 to percent (as elongation). While this is less
than that of most engineering materials, it is adequate for
most coating applications. Thin films of the deposit can
be bent completely around themselves without fracture, and
the coating has been used successfully for springs and
bellows. Electroless nickel, however, should not be applied
to articles which subsequently will be bent or drawn. Severe
deformation will crack the deposit, reducing corrosion and
abrasion resistance. With lower phosphorus deposits, or
with deposits containing metallic or sulfur impurities,
ductility is greatly reduced and may approach zero 5,8. The
effect of phosphorus content upon the strain at fracture of
electroless nickel coatings is also shown in Figure 10
22
Hardening type heat treatments reduce both the strength
and the ductility of electroless nickel deposits. Exposure
to temperatures above 2200C (4200F) cause a 80 to 90 percent
reduction in strength and can destroy ductility, especially
in lower phosphorus coatings. This is illustrated by Figure
11, which shows the effect of different one hour heat treat-
ments on the elongation at fracture of brass panels coated
with a 6 percent phosphorus electroless nicke1
2 0
Because
of their high phosphorus content and ~ purity, the effect of
heat treatment on the ductility of deposits is not as
pronounced. The ductility of coatings is not significantly
reduced until it is heated to above 260C (SOOF)5.
FIGURE 11
Temperature, of
1400 1000 600 200
a
2
"'
\
It
1
I
-,
.J
a
Effect of heat treatment
on the ductility of a 6
percent phosphorus
electroless nickel.
200 400 600 800
Temperature, DC
The modulus of elasticity of non-heat treated electroless nickel
coatings containing 10 to 11 percent phosphorus is about 200 GPa
(28XI0
6psi)
and is very similar to that of stee1
2,22.
The modulus of deposits containing 7 to 8 percent phosphorus is
only about 120 GPa (18xl0
6psi)
and is more similar to that of
copper alloys. Heat treating electroless nickel coatings at
temperatures above 2000C (4000F) causes their modulus of elas-
ticity to increase significantly2,23.
HARDNESS AND WEAR RESISTANCE
Two of the most important properties for many applications
are hardness and wear resistance. As deposited, the micro-
hardness of electroless nickel coatings is about 500 to
600 VHNIOO. This is approximately equal to 48 to 52 HRC
and equivalent to many hardened alloy steels. Heat treat-
ment causes these alloys to age harden and can produce
hardness values as high as 1100 VHNIOO. This is equal to
most commercial hard chromium coatings. Figure 12 shows
the effect of different 1 hour heat treatments on the
hardness of electroless nickel deposits
2
, 5
-----------------------------------------
FIGURE 12
Temperature, of
700
1200
600
11100
500
600
400
600
300
400
200
200
"0
00
,
I'
'\
0
i
,
I
\
II
""
1'-0-
0

0
/
V
.-
0
900
60
70
11
",
'"
>

80
j
Effect of heat treatment
at different temperatures
on the hardness of
Electroless Nickel.
Temperature,OC
For some applications, high temperature treatments cannot be
tolorated because of part warpage or because of their effect
on the substrate. For these, it is sometimes possible to use
longer times and lower temperatures to obtain the desired
hardness. This is illustrated by Figure 13, which shows the
effect of different treatment periods on the hardness of
coatings
s.
Treatments at 340C (650F) for 4 to 6 hours and at 290C
(550F) for 10 to 12 hours are commonly used for electroless
nickel deposits. These can produce hardness values of 950
to 1000 VHNIOO. Treatments at 260C (500F) are also
occasionally used, although the resulting hardness is lower.
At temperatures of 230C (450F) and below, only a minimal
increase in hardness is obtained. Accordingly such treat-
ments are only rarelr used, except for hydrogen relief or
adhesion improvement .
FIGURE 13
0
:--<:...00 -c (750 'F}
0
/"
~ C (55SoF\
I
0
/
~ I ~
/ /
7"
310 "c (590 "Fl
-
-
f...-
0
I
/'
--"0"c 1500 i"
-:
0
(/
230 o ~ (445 'Fl
/'
0
f(
200C1390Ff
/'
0
0
90
so
60
40
110
100
i: 80
Effect of different
heat treatment periods
on the hardness of
Electroless
Nickel.
4 11 16 10 24
Treatment period, h
Electroless nickel coatings also have excellent hot hardness.
Up to about 4000C (7500F) the hardness of heat treated electro-
less nickel is equal to or better than that of hard chromium
coatings. As-deposited coatings also retain their hardness
to this temperature, although at a lower level. The effect
of elevated temperature on a 10 percent phosphorus coating
is shown in Figure 14 24,25
FIGURE 14
800 700
600 SOD
.00
400
600
TlISttemperature, OF
Test temperature. c
300
400 200
00
1000 1100 1400
0 ---
.....
z--,':<::' treated "400'C (750 'FI
........
0
....
0
.... \
,
As deposited
'"
-<,Chromium
~
~
-,
"
0
"
<,
~
"....
0
.... ,
-..;:::
"
0 100 100
80
40
20
11
100
Effect of temperature
on the elevated
temperature hardness
of a 10 percent
phosphorus electroless
nickel.
Because of their high hardness, electroless nickel coatings
have excellent resistance to wear and abrasion, both in the
as-deposited and hardened conditions. Laboratory tests have
shown fully hardened coatings to have wear resistance equal
to hard chromium under both dry and lubricated conditions.
This is illustrated by Table 1, which shows the results of
typical Taber Abraser Wear tests of electroless nickel
coatings, and compares them to electroplated nickel and
chromium26 ,27 ,28. The excellent resistance of electroless
nickel often allows it to replace high alloy materials and
hard chromium.
TABLE 1
COMPARISON OF THE TABER ABRASER RESISTANCE
OF DIFFERENT ENGINEERING COATINGS
COATINJ HEAT TREA'lMENT TWI, mg/1000
Cycles (1)
Watts Nickel None 25
Electroless Ni-9%P None 17
Electroless Ni-9%P 300
oC/l
hr 10
Electroless Ni-9%P 500
oC/l
hr 6
Electroless Ni-9%P 650
oC/l
hr 4
Electroless Ni-5%B None 9
Electroless Ni-5%B 400
oC/l
hr 3
Hard Chromium None 3
(1) Taber Wear Index, CS-IO abraser wheels, 1000 gram load,
determined as average weight loss per 1000 cycles for
total test of 6000 cycles.
Tests with electroless nickel coated vee-blocks in a Falex
Wear Tester have confirmed a similar relation between heat
treatment and wear, and shown the coating to be more resis-
tant than hard chrome under lubricated wear conditions.
This is illustrated by Table 2 for an electroless nickel
containing approximately 9 percent phosphorus.
TABLE 2
COMPARISON OF THE FALEX WEAR RESISTANCE
OF CHROMIUM AND ELECTROLESS NICKEL COATINGS
COATII'G PLATED V-BLOCKS UNPLATED STEEL PINS
Heat Hardness, Wear Wear, mg (1)
Treatment
"lHN
mg (1)
Chromium None 1100 0.5 1.9
Electroless Nickel None 590 6.6 0.2
Electroless Nickel 290
oC/2
hrs 880 1.2 0.1
Electroless Nickel 290
oC/16
hrs 1050 0.4 0.1
Electroless Nickel 400
oC/l
hr 1100 0.5 0.2
Electroless Nickel 540
oC/l
hr 750 1.4 0.1
(1) Falex Wear Test under
white oil lubricant.
at 60 HRC hardness.
180 kg (400 lb) for 40 minutes with
Unplated pins were SAE 9310 steel
The effect of phosphorus content upon the wear experienced
by electroless nickel coatings under lubricated conditions is
summarized in Figure 15. These rotating ball tests showed that
after heat treatment, high phosphorus deposits like i pro-
vide the best resistance to adhesive wear
2 9,30.
~
~
"
5
;"
>
~
..
0
E
~ . e
~
,
'0
>
0
8
6
.....e.:. deposited-

I
2
il
r-,
--
r-
1
1
8
6 250 c{480 of} for 1 h_

"::
<,
2
400 "c (750 of) for 1 ~
1
1
,
6

<,
2
1
I
. 0.00
o.
0.00
I.
O.
o.
o.
"E
~ o.
~ . 0.0
0.0
~ 0.0
..
~ 0.0
e
~ D.ll
~ 0.00
non
0.00
Effect of phosphorus
content on the wear of
electroless nickel
coatings in rotating
ball tests.
FIGURE 15
111 12
Phosphorus content. %
FRICTIONAL PROPERTIES
The frictional characteristics of electroless nickel coatings
are excellent. Their phosphorus content provides a natural
lubricity, which helps to minimize heat buildup and reduces
scoring and galling and which can be very useful for
applications such as plastic molding.
The coefficient of friction for electroless nickel versus
steel is about 0.13 for lubricated conditions and 0.4 for
unlubricated conditions. This is approximately 20 percent
lower than chromium, one-half of that of steel, and much
lower than aluminum or stainless steel. The frictional
properties of these coatings vary little with either
phosphorus content or with heat treatment
2
, 2 6 , 30 .
SOLDERABILITY AND WELDABILITY
Electroless nickel coatings can be easily soldered and are
commonly used in electronic applications to facilitate soldering
of light metals, like aluminum. For most components, mildly
activated rosin (RMA) flux is specified together with convention-
al tin-lead solder. Preheating the component to 100 to 110C
(2100 to 230F) will improve the ease and speed of joining.
with moderately oxidized surfaces, such as those resulting from
steam aging, activated rosin (RA) flux is usually required to
obtain wetting of the coating
2
, 31
Welding of electroless nickel coated components is more difficult
due to the low welding point of the alloy and because phosphorus
can diffuse into an embrittle steel. Some success has been re-
ported using special high purity stainless steel electrodes and
inert gas shielding. with piping high nickel backup rings are
also sometimes used
2

CORROSION RESISTANCE
Electroless nickel is a barrier coating, it protects its
substrate by sealing it off from the environment, rather
than by sacrificial action. Because of its amorphous
nature and passivity, however, the corrosion resistance
of the coating is excellent and in many environments
superior to that of pure nickel or chromium alloys.
Amorphous alloys generally have better resistance to attack
than equivalent polycrystalline materials, because of their
freedom from grain or phase boundaries, and because of the
glassy films which form on and passivate their surfaces.
Effect of Environment. When properly applied,
Electroless Nickel is almost totally resistant to alkalies,
to salt solutions and brines, to chemical and petroleum
and to all types of hydrocarbons and solvents.
deposits also have good resistance to ammonia solutions,
to organic acids, and to reducing inorganic acids. The are
only significantly attacked by strongly oxidizing media 2.
Some examples of the corrosion experienced in different
environments is shown in Table 3
2,9,32
Effect of Composition. The corrosion resistance of an
electroless nickel coating is a function of its composition.
Most deposits are naturally passive and very resistant to
attack in most environments. Their degree of passivity
(and corrosion resistance), however, is qreatly affected by
their phosphorus content. Alloys containing more
than 10 percent phosphorus are generally more resistant to
attack than those with lower phosphorus contents 9,15. This
is illustrated by Figure 16, which compares the corrosion
experienced by electroless nickel coatings containing S to
percent phosphorus in aerated, 6 percent citric acid
at SOoC (120 F) 33.
FIGURE 16
14
Effect of phosphorus
content on the corrosion
of electroless nickel
coatings.
12
10

12
10

5 4
0,;-
PHOSPHORUS CONTENT, WT. PERCENT
CORROSION OF
TABLE 3
ELECTROLESS NICKEL IN
VARIOUS ENVIRONMENTS
EN\lI:ROtMENT TEMPERATURE CORROSION RATE
c Ilm/ y mpy
Acetic Acid, Glacial 20 0.8 0.03
Acetone 20 0.08 0.003
Aluminum Sulfate, 27% 20 5 0.2
Armnonia, 25% 20 16 0.6
Ammonium Nitrate, 20% 20 15 0.6
Ammonium Sulfate, Saturated 20 3 0.1
Benzene 20 Nil Nil
Brine, ~ Salt, CO
2
Saturated 95 5 0.2
Brine, 3'>% Salt, H
2
S Saturated 95 Nil Nil
Calcium Chloride, 42% 20 0.2 0.01
Carbon Tetrachloride 20 Nil Nil
Citric Acid, Saturated 20 7 0.3
Cupric Chloride, 5% 20 25 1.0
Ethylene Glycol 20 0.6 0.02
Ferric Chloride, 1% 20 200 8.0
lOrmic Acid, 88% 20 13 0.5
Hydrochloric Acid, 5% 20 24 0.9
Hydrofluqric Acid,2% 20 27 1.1
Lactic Acid, 85% 20 1 0.04
Lead Acetate, 36% 20 0.2 0.01
Nitric Acid, 1% 20 25 1.0
Oxalic Acid, 10% 20 3 0.1
Phenol, 90% 20 0.2 0.01
Phosphoric Acid, 85% 20 3 0.1
Potassium Hydroxide, 50% 20 Nil Nil
Sodium Carbonate,Saturated 20 1 0.04
Sodium Hydroxide, 45% 20 Nil Nil
Sodium Hydroxide, 50% 95 0.2 0.01
Sodium SUlfate, 10% 20 0.8 0.03
Sulfuric Acid, 65% 20 9 0.4
Water, Acid Mine, 3.3 pH 20 7 0.3
Water, Distilled, N
2
deaerated 100 Nil Nil
Water, Distilled, O
2
Saturated 95 Nil Nil
Water, Sea (3'>% Salt) 95 Nil Nil
In these tests, corrosion of the deposit was only about
one half of that of the lower phosphorus coatings.
Often, the tramp constituents present in an electroless nickel
are even more important to its corrosion resistance than its
phosphorus content. Most coatings are applied from baths
inhibited with lead, tin, cadmium or sulfur. Codeposition of
these elements in more than trace amounts causes a severe
reduction in the coating's passivity and corrosion resistance.
This is illustrated by Table 4, which shows the results of
corrosion tests with 6 different electroless nickel deposits
in C02 saturated, percent salt brine at 9SoC (200
0F)9.
TABLE 4
EFFECT OF COMPOSITION ON CORROSION RESISTANCE
OF ELECTROLESS NICKEL IN CO2 SATURATED,
PERCENT SALT BRINE AT 9SoC
DEPOSIT PHOSPHOR LS OTHER CORROSION RATE
CONTENT, % ELEMENTS, % lJro/y ropy
----
ELNIC 10.2 trace 5 0.2
B 11.8 0.04 Sn 7 0.3
C 8.3 0.05 Cd 24 0.9
D 10.3 0.12 Pb 15 0.6
E 8.0 0.13 S 15 0.6
F 10.4 0.05 Pb and 11 0.4
0.08 Cd
Similar tests in 10 percent RCl at ambient temperature
showed losses ranging from lS lJm/v (0.6 mpy) for to
660 umz'y (26 mpy) for Deposit D..
The primary difference between these deposits was not their
phosphorus content, but their baths' inhibitor.
Deposits B, D. and F all contained more than 10 percent
phosphorus.
B to F, were applied
sulfur and contained
Deposits
from baths inhibited with metals or
significant amounts of these elements
9.
Effect of Heat Treatment. One of the most important variables
effecting the corrosion of electroless nickel is its heat
treatment. As electroless nickel deposits are heated to
temperatures above 220 to 260C (420 to 500F) nickel phosphide
particles begin to form, reducing the phosphorus content of
the remaining material. This reduces the coating's corrosion
resistance. The particles also create small active/passive
corrosion cell$, further contributing to the deposit's
destruction. The effect of these changes is illustrated by
Table 5, which shows the results of tests with deposits,
heat treated to represent different commercial treatments and
then exposed to 10 percent HCl at ambient tempertaure. A
secondary effect of heat treating is that the deposit shrinks
as it hardens, which can crack the coating and expose the
substrate to attack. A cross-sectional view of the cracks
throuqh an electroless nickel coatinq after heat treatment
at 400C (7500F) is shown in Figure 7
9

FIGURE 17
Cross sectional view
of a 75 rom thick _
electroless nickel de-
posit after heat treat-
ment at 400C for 1
hour. Cracks formed
due to shrinkage of
the deposit.
lOOX magnification.
Etched in 2% nital.
TABLE 5
THE EFFECT OF HEAT TREATMENT
ON THE CORROSION OF ELECTROLESS NICKEL
IN 10% HCl
HEAT TREATMENT DEPOSIT CORROSION RATE
HARDNESS, u mz'y ropy
vllNIOO__
None 480 15 0.6
190C (375 E) for 11, hours 500 20 0.8
290C (550F) for 6 hours 900 1900 75
290C (550E) for 10 hours 970 1400 55
340C (650E) for 4 hours 970 900 35
400C (750 F) for 1 hour 1050 1200 47
Baking at 190C (375F), like that used for hydrogen embrittle-
ment relief, caused no significant increase in corrosion.
Hardening, however, caused the coating's corrosion rate to
increase from 15 ).Im/y (0.6 mpy) to more than 900 ).Im/y (35 mpy)
Tests in other environments showed a similar reduction in resistance
after hardening. Where corrosion resistance is required, hardened
coatings should not be used
9
SUMMARY OF THE PROPERTIES OF ELECTROLESS NICKEL
COMPOSITION
STRUCTURE
INTERNAL STRESS
DENSITY
MELTING POINT
ELECTRICAL RESISTIVITY
THERMAL CONDUCTIVITY
MAGNETIC SUSCEPTABILITY
TENSILE STRENGTH
DUCTILITY
MODULAS OF ELASTICITY
COEFFICIENT OF THERMAL
EXPANSION
ADHESION STRENGTH
HARDNESS, AS DEPOSITED
IMRDNESS, HEAT TREATED
(400C/l hr)
COEFFICIENT OF
FRICTION VS. STEEL
TABER WEAR RESISTANCE,
AS DEPOSITED
TABER WEAR RESISTANCE
HEAT TREATED (400C/l hr)
CORROSION RESISTANCE
RND: lt
December 31, 1980
Revised
May 19, 1983
Alloy of 10 to 11 percent phosphorus
dissolved in nickel, containing less
than 0.05 percent other impurities
Completely amorphous, without any crystal
or phase structure, lamination or
internal segregation
During heat treatment, particles of Ni3P
precipitate and the coating crystallizes
20 to 30 MFa (2.5 to 4 ksi) compressive
7.75 g/cm
3
90 ~ Q c m as deposited
0.08 W/cm-oK (4.6 Btu/ft-hr-OF), as deposited
-'
Approximately 10 mks
>700 MPa (>100 ksi), as deposited
1 to l ~ percent elongation, as deposited
6
200 GPa (28 x 10 psi)
300 to 400 MPa (40 to 60 ksi)
480 to 500 VHN
10 0
1000 to 1100 VHN
100
0.13 (lubricated) to 0.4 (non-lubricated)
18 to 20 mg/1000 cycles
10 to 12 mg/1000 cycles
A barrier coating with excellent resistance
to attack by all but the most severely
oxidizing environments
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